CN110337471A - SiO2Coating is carrying the purposes in water cooling system - Google Patents

SiO2Coating is carrying the purposes in water cooling system Download PDF

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Publication number
CN110337471A
CN110337471A CN201880007207.8A CN201880007207A CN110337471A CN 110337471 A CN110337471 A CN 110337471A CN 201880007207 A CN201880007207 A CN 201880007207A CN 110337471 A CN110337471 A CN 110337471A
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Prior art keywords
coating
priming coat
purposes
apply
method described
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CN201880007207.8A
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Chinese (zh)
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T·克雷泽尔迈尔
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Prattock International
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Prattock International
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/002—Pretreatement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B05D7/222—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of pipes
    • B05D7/225—Coating inside the pipe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/548—No curing step for the last layer
    • B05D7/5483—No curing step for any layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto 
    • B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
    • B08B9/027—Cleaning the internal surfaces; Removal of blockages
    • B08B9/032—Cleaning the internal surfaces; Removal of blockages by the mechanical action of a moving fluid, e.g. by flushing
    • B08B9/0321—Cleaning the internal surfaces; Removal of blockages by the mechanical action of a moving fluid, e.g. by flushing using pressurised, pulsating or purging fluid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/006—Constructions of heat-exchange apparatus characterised by the selection of particular materials of glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2504/00—Epoxy polymers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Silicon Compounds (AREA)

Abstract

The present invention relates to nanoscale SiO2The method that grain coating prevents the purposes denuded and deposited and this coating of production in carrying water cooling system.

Description

SiO2Coating is carrying the purposes in water cooling system
The present invention relates to nanoscale SiO2Grain coating prevents the purposes of abrasive corrosion and deposition in carrying water cooling system, And cooling water pipe/pipeline method is coated by means of this particle.Such coating is especially suitable for water-cooled firepower The cooling system in power plant.
The cooling water system in thermal power plant most commonly uses the surface water acquired from peripheral region to run, that is, uses river Water and seawater.Due to containing suspended material and dissolution substance in cooling water, these power plants and system by many external actions, It especially must endure as mechanical, chemistry and electrochemistry stress.
Due to the solid particle that cooling medium carries, such as sand, mechanical stress can be encountered.Chemical stress is situated between derived from cooling Whether the property of matter, such as medium contain salt, alkaline matter or acidic materials.Specifically mentioned seawater for cooling purposes herein Or the well-known corrosiveness of the river water seriously polluted.
In this regard, electrochemical corrosion or galvanic corrosion refer to by metal interface, especially in tube sheet and cooling The corrosion hazards for forming galvanic couple element in transitional region between agent pipe and occurring, the corrosion pass through such as seawater or saliferous river The conductive fluids such as water and significantly reinforce.
Thermal stress caused by additionally, there are the temperature difference due to being generated between cooling medium and steam to be condensed, the temperature difference 100 DEG C may far be surpassed, and lead to mechanical stress, especially in the region that coolant hose is involved in tube sheet.In addition, raised Temperature can increase the corrosiveness of acid, salt and other dissolution substances.
Further, since the deposition of undesirable substance, algae are formed in pipe, the function of steam condenser is caused to be damaged Evil, this is especially promoted by the rough region such as rough region caused by corroding.As a result, corrosion and depositional phenomenon not only with The runing time of steam condenser and accelerate, and due to it is already existing corrosion and deposition starting point quantity constantly increase Add, they even more deteriorate.
Therefore, make great efforts to provide the corrosion-inhibiting coating of plastic material for steam condenser in early stage.In particular, at this time It is used for the coating based on epoxy resin.Initially, predominantly tube sheet provides such coating, but this method cannot solve Particular problem certainly relevant to the generation of tube inner corrosion and deposition.Later, tube inlet and exit region, mesh are also applied a layer to Be protect this extrahazardous transitional region.The measure of the above-mentioned type can be from such as GB-A-1 125 157, DE 1 939 665 U, DE 7 702 562 U, EP 0 236 388 know in A and 94 106 304 A of EP.
For a long time, the coated inside of coolant hose causes problem since pipeline is considerably long and diameter is small, but simultaneously Solves this problem.In this respect, 2012/045466 A1 of WO 97/197058 A1 and WO can be referred to.They are retouched The device stated can be applied a layer on the inner wall of coolant lines by controlled application system and special coating nozzle.
It is described in such as 95/29375 A1 of WO based on epoxy resin-amine hardener system coating.
Itself is had been proven that in principle by traditional cooling water system coating of plastic material, but needs periodically to turn over It repairs.The abrasive corrosion in the metal for extending to the coolant hose of coating is had shown that in many cases, especially works as base When the operation of corrosivity cooling water.When there are advantageous heat condition, also biological growth frequent occurrence.In addition, accordingly polluting Cooling water in the case where, also frequently encounter mineral deposition.This means that must clean and coat coolant hose again.Especially Be, it is known that plastic compound be not suitable for for a long time bear abrasive corrosion.
Therefore, it is necessary to coat load water cooling system, especially coolant hose in this way, so that they have more Long service life and offer preferably prevents abrasive corrosion and prevents the protection of deposition.In particular, this coating should not mistake Divide the thermal conductivity of the damage tube wall that coating is be applied to.
Use the nanoscale SiO mentioned for the first time above2Coating realizes this purpose.
Within the meaning of the present invention, abrasive corrosion is defined as any kind of corruption for causing cooling system wall to remove and degrade Erosion.
The nanoscale SiO according to the present invention for proposing to use2Particle formed in the surface with the particle disposal≤ 500nm, the preferably thin silicon dioxide layer of 50-300nm.This is not construed as the GPF (General Protection False measure for preventing oxidation；Oxide skin(coating) exists Many aspects are suitable for protecting following metal from further attack.More precisely, coating actually enclosed watch Face prevents from adhering to, and slows down abrasive corrosion due to its hardness.
No matter when mention deposition, it means that including promote to slow down or prevent coolant flow in a cooling system and into One step is hindered through both the mineral deposition of the heat transmitting of cooling system wall and biogenic deposit.
In itself, by nanoscale SiO2Coating made of particle is known.For example, they are for coating mineral Surface and biological surface, so that they have soil resistance.With the help of this coating, protection of effectively scribbling may be implemented, However, it is also possible to take equipment protection measure by mixing biocidal activity substance.Contain SiO by applying2The water of particle Property sol-gel generates coating, wherein SiO2The common size of particle is less than 10nm.The example can be in publication EP 1 826 It is found in 10 2,007 060 320 A1 of 248 A1 and DE, the publication also describes the production of the sol-gel based on silane It is raw.Specifically and explicitly with reference to these generate process.
Apply aqueous coating solution especially by spraying.In this respect, film thickness is less than 500nm, and usually 50- The range of the range of 300nm, especially 80-150nm.It has been found that biggish film thickness is difficult to realize, because once being applied Aqueous solution be consolidated into solid layer, the hydrophily and hydrophobicity of these layers also hinder and limit the adherency of identical material.Assuming that Association and polymerization process occur during application, this leads to the non-porous covering of coating surface.
It has been proved that the surface of coating is largely inertia to mechanical stress, chemical stress and electrochemistry stress 's.Due to the hydrophily and hydrophobicity of coating, the adherency of mineral material and biomaterial and deposition are seriously hampered, therefore with The surface that this mode coats keeps without hindrance, and fluid can pass through without blockage coolant lines for a long time.Coating It is non-porous, therefore they reliably protect following metal base (or priming coat), and will not significantly affect and apply The thermal conductivity of the wall of this coating.
Coating can be especially advantageously applied on water guide coolant lines, but it can also be used in its of cooling system On his component, such as tube sheet, valve, pump etc..In principle, this nanoscale SiO2Grain coating can be used for all water guiding systems, i.e., Such as waterpipe/pipe, heat exchanger, heating system, arrangement for quickly heating water, sewage treatment plant, water treatment plant, seawater desalting plant, especially It is to be also used to supply line and similar system.
The coating of application proposed by the invention can also be used in the deactivation on surface, also especially coolant lines surface Deactivation, in the desalinator that these surfaces are used to be run according to flash principle.
Applying nanoscale SiO2Before particle, applying priming coat can be advantageous, especially if to be coated is cold But water system is older and has shown that signs of corrosion, and it is meaningful thus to fill up corrosion area.For this purpose, epoxy amine Hardener system it is verified oneself, as example described in publication WO 95/29375A1.Several layers of this primary coat can be applied Layer, wherein the film thickness in coolant lines is generally at least 80 μm, and can achieve 2000 μm or bigger on tube sheet.80 μm to 250 μ ms coating be commonly used in coolant lines.
The invention further relates to the methods that coating proposed by the present invention is applied to cooling water pipeline, and the method includes following Step:
(a) pipeline is cleaned with water under high pressure,
(b) if it is considered to being necessary or advantageous, apply priming coat, and
(c) apply by nanoscale SiO2Aqueous sol-gel of particle composition, consolidation forms SiO on the surface2Layer.
In general, applying coating by spraying.
It is carried out under high pressure with water cleaning pipeline, pressure used is up to 2500 bars.For example, publication WO 2012/ 045466A1 proposes and describes a kind of cleaning systems equipped with the nozzle sprayed backward, and the nozzle sprayed backward is with reversed Traveling mode operates and has 60 ° -120 ° of the jet angle relative to coolant hose longitudinal direction.This nozzle not only can be with For cleaning purposes, it and can be used for applying coating material, provide an advantage in that, i.e., removed by cleaning process Material be discharged with water flow so that coating procedure is interference-free, and coating is not by the movement of nozzle and application hose Damage.
The monolayer material used according to the invention applied in single work step is enough.
Apply priming coat mainly for the treatment of the older coolant hose for having shown that corrosion and spot corrosion sign.For can be with One or more layers priming coat is made of and can applied one or more layers, it is described above to be based on epoxy resin-amine hardener body The material of system is specially suitable.The film thickness of priming coat is as described in above with respect to pipe coating.
Apply aqueous sol-gel by spraying to generate SiO2Layer, can be used said nozzle for this purpose, however, The nozzle is run under rather low pressure.The application pressure for being commonly used for the priming coat is up to 500 bars, but for applying Add the sol-gel, pressure is only up to about 10 bars.
The details of coating unit and coating method is described in publication WO2012/045466A1, and introduction is clearly It is included herein.

Claims (17)

1. including nanoscale SiO2The coating of particle is in carrying water cooling system for preventing the purposes of abrasive corrosion and deposition.
2. purposes according to claim 1, it is characterised in that film thickness≤500nm of the coating.
3. purposes according to claim 2, it is characterised in that range of the film thickness of the coating in 50-300nm.
4. purposes according to any one of the preceding claims, it is characterised in that the load water cooling system is to pass through river water Or the cooling water system of seawater operation.
5. purposes according to any one of the preceding claims, it is characterised in that the cooling system be thermo-power station pipe and Pipeline.
6. purposes according to any one of the preceding claims, it is characterised in that by nanoscale SiO2The painting of particle composition Layer is lower to apply priming coat.
7. purposes according to claim 6, it is characterised in that the priming coat is formed by several layers.
8. purposes according to claim 6 or 7, it is characterised in that epoxy resin-amine hardener system is used as priming coat.
9. purposes a method according to any one of claims 6-8, it is characterised in that the film thickness of the priming coat at 80 μm extremely 2000 μm of range.
10. the method for coating cooling water pipeline, comprising the following steps:
(a) cooling water pipeline is cleaned with water under high pressure；
(b) if it is considered to being necessary or advantageous, apply priming coat；
(c) apply by nanoscale SiO2Aqueous sol-gel of particle composition, consolidation forms SiO on the surface2Layer.
11. according to the method described in claim 10, it is characterized in that carrying out the cleaning under up to 2500 bars of pressure.
12. method described in 0 or 11 according to claim 1, it is characterised in that apply priming coat under up to 500 bars of pressure.
13. method described in any one of 0-12 according to claim 1, it is characterised in that apply institute under up to 10 bars of pressure State aqueous sol-gel.
14. method described in any one of 0-13 according to claim 1, it is characterised in that the cleaning of the cooling water pipeline and The application of the priming coat and the application of the aqueous sol-gel are the nozzles by being designed to operate with negative line feed It carries out, the jet angle of the nozzle is in the range relative to 60 ° -120 ° of pipe/pipeline longitudinal direction to be processed.
15. method described in any one of 0-14 according to claim 1, it is characterised in that the SiO2Film thickness < 500nm of layer, It is preferred that in the range of 50-300nm.
16. method described in any one of 0-15 according to claim 1, it is characterised in that apply at least one priming coat, film thickness Spend the range at 80 μm to 2000 μm.
17. the method for any one of 0-16 according to claim 1, it is characterised in that apply epoxy resin-amine hardener system and make For priming coat.
CN201880007207.8A 2017-01-18 2018-01-18 SiO2Coating is carrying the purposes in water cooling system Pending CN110337471A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102017100946.9 2017-01-18
DE102017100946.9A DE102017100946A1 (en) 2017-01-18 2017-01-18 Use of SiO2 coatings in water-carrying cooling systems
PCT/EP2018/051203 WO2018134302A1 (en) 2017-01-18 2018-01-18 Use of sio2 coatings in water-carrying cooling systems

Publications (1)

Publication Number Publication Date
CN110337471A true CN110337471A (en) 2019-10-15

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Country Status (9)

Country Link
US (1) US11708497B2 (en)
EP (1) EP3574054B1 (en)
JP (1) JP2020506298A (en)
KR (1) KR20190112724A (en)
CN (1) CN110337471A (en)
CA (1) CA3050173A1 (en)
DE (1) DE102017100946A1 (en)
UA (1) UA124984C2 (en)
WO (1) WO2018134302A1 (en)

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